US20100197483A1 - Ionic liquid catalyst regenerated using a regeneration metal in the presence of added hydrogen - Google Patents
Ionic liquid catalyst regenerated using a regeneration metal in the presence of added hydrogen Download PDFInfo
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- US20100197483A1 US20100197483A1 US12/759,424 US75942410A US2010197483A1 US 20100197483 A1 US20100197483 A1 US 20100197483A1 US 75942410 A US75942410 A US 75942410A US 2010197483 A1 US2010197483 A1 US 2010197483A1
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- United States
- Prior art keywords
- ionic liquid
- liquid catalyst
- catalyst
- conjunct polymers
- regeneration
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 207
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 149
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 230000008929 regeneration Effects 0.000 title claims abstract description 43
- 238000011069 regeneration method Methods 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 23
- 239000001257 hydrogen Substances 0.000 title claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 122
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 19
- 230000000694 effects Effects 0.000 claims abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- 238000005804 alkylation reaction Methods 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 230000029936 alkylation Effects 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 239000011831 acidic ionic liquid Substances 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 3
- 230000021736 acetylation Effects 0.000 claims description 3
- 238000006640 acetylation reaction Methods 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 238000006471 dimerization reaction Methods 0.000 claims description 3
- 238000006384 oligomerization reaction Methods 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 51
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 21
- 239000012071 phase Substances 0.000 description 17
- 230000007062 hydrolysis Effects 0.000 description 16
- 238000006460 hydrolysis reaction Methods 0.000 description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 15
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- -1 ammonium cations Chemical class 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 6
- 150000007517 lewis acids Chemical class 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 239000001282 iso-butane Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- FMQZFKHJACCVMS-UHFFFAOYSA-G 1-butylpyridin-1-ium;tetrachloroalumanuide;trichloroalumane Chemical compound [Cl-].Cl[Al](Cl)Cl.Cl[Al](Cl)Cl.CCCC[N+]1=CC=CC=C1 FMQZFKHJACCVMS-UHFFFAOYSA-G 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012455 biphasic mixture Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- YBPJNJSKPUAMKZ-UHFFFAOYSA-N decane Chemical compound CCCCCCCCC[CH2-] YBPJNJSKPUAMKZ-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N di-methylphenol Natural products CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007871 hydride transfer reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000011829 room temperature ionic liquid solvent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
Definitions
- the present invention relates to methods for the regeneration of catalysts and more specifically to the regeneration of ionic liquid catalysts.
- Ionic liquids are liquids that are composed entirely of ions.
- the so-called “low temperature” Ionic liquids are generally organic salts with melting points under 100 degrees C., often even lower than room temperature.
- Ionic liquids may be suitable for example for use as a catalyst and as a solvent in alkylation and polymerization reactions as well as in dimerization, oligomerization acetylation, metatheses, and copolymerization reactions.
- ionic liquids One class of ionic liquids is fused salt compositions, which are molten at low temperature and are useful as catalysts, solvents and electrolytes. Such compositions are mixtures of components which are liquid at temperatures below the individual melting points of the components.
- Ionic liquids can be defined as liquids whose make-up is entirely comprised of ions as a combination of cations and anions.
- the most common ionic liquids are those prepared from organic-based cations and inorganic or organic anions.
- the most common organic cations are ammonium cations, but phosphonium and sulphonium cations are also frequently used.
- Ionic liquids of pyridinium and imidazolium are perhaps the most commonly used cations.
- Anions include, but not limited to, BE 4 ⁇ , PF 6 ⁇ , haloaluminates such as Al 2 Cl 7 ⁇ and Al 2 Br 7 ⁇ , [(CF 3 SO 2 ) 2 N)] ⁇ , alkyl sulphates (RSO 3 ⁇ ), carboxylates (RCO 2 ⁇ ) and many other.
- the most catalytically interesting ionic liquids are those derived from ammonium halides and Lewis acids (such as AlCl 3 , TiCl 4 , SnCl 4 , FeCl 3 . . . etc). Chloroaluminate ionic liquids are perhaps the most commonly used ionic liquid catalyst systems.
- Examples of such low temperature ionic liquids or molten fused salts are the chloroaluminate salts.
- Alkyl imidazolium or pyridinium salts for example, can be mixed with aluminum trichloride (AlCl 3 ) to form the fused chloroaluminate salts.
- AlCl 3 aluminum trichloride
- the use of the fused salts of 1-alkylpyridinium chloride and aluminum trichloride as electrolytes is discussed in U.S. Pat. No. 4,122,245.
- Other patents which discuss the use of fused salts from aluminum trichloride and alkylimidazolium halides as electrolytes are U.S. Pat. Nos. 4,463,071 and 4,463,072.
- liquid clathrate compositions useful as reusable aluminum catalysts in Friedel-Crafts reactions.
- the liquid clathrate composition is formed from constituents comprising (i) at least one aluminum trihalide, (ii) at least one salt selected from alkali metal halide, alkaline earth metal halide, alkali metal pseudohalide, quaternary ammonium salt, quaternary phosphonium salt, or ternary sulfonium salt, or a mixture of any two or more of the foregoing, and (iii) at least one aromatic hydrocarbon compound.
- Aluminum-containing catalysts are among the most common Lewis acid catalysts employed in Friedel-Crafts reactions. Friedel-Crafts reactions are reactions which fall within the broader category of electrophylic substitution reactions including alkylations.
- ionic liquid catalysts become deactivated, i.e. lose activity, and may eventually need to be replaced.
- ionic liquid catalysts are expensive and replacement adds significantly to operating expenses by in some cases requiring shut down of an industrial process.
- One of the heretofore unsolved problems impeding the commercial use of chloroaluminate ionic liquid catalysts has been the inability to regenerate and recycle them.
- the present invention provides methods to regenerate acidic chloroaluminate ionic liquid catalysts overcoming this obstacle and paving the way for the practical, commercial use of these environmentally friendly catalysts.
- the present invention provides a process for regenerating a used acidic ionic liquid catalyst comprising contacting the used ionic liquid catalyst with at least one metal in a regeneration zone in the presence of added hydrogen under regeneration conditions for a time sufficient to increase the activity of the ionic liquid catalyst.
- regeneration is conducted in the presence of a hydrocarbon solvent.
- the present invention relates to a process for the regeneration of spent or deactivated acidic ionic liquid-based catalysts i.e. those catalysts which have lost all or some of their catalytic activity.
- the present process is being described and exemplified with reference certain specific ionic liquid catalysts and processes catalyzed thereby, but such description is not intended to limit the scope of the invention.
- the methods described may be applied to other catalysts and processes by those persons having ordinary skill based on the teachings, descriptions and examples included herein.
- the specific examples used herein refer to alkylation processes using ionic liquid systems, which are amine-based cationic species mixed with aluminum chloride.
- the ionic liquid catalyst is generally prepared to full acidity strength by mixing one molar part of the appropriate ammonium chloride with two molar parts of aluminum chloride.
- the catalyst exemplified for the alkylation process is a1-alkyl-pyridinium chloroaluminate, such as 1-butyl-pyridinium heptachloroaluminate.
- a strongly acidic ionic liquid is necessary for isoparaffin alkylation, e.g. isoparaffin alkylation.
- aluminum chloride which is a strong Lewis acid in a combination with a small concentration of a Broensted acid, is a preferred catalyst component in the ionic liquid catalyst scheme.
- conjunct polymers are polyunsaturated cyclic, polycyclic and acyclic molecules formed by concurrent acid-catalyzed reactions including, among others, polymerization, alkylation, cyclization, and hydride transfer reactions.
- Conjunct polymers consist of unsaturated intricate network of molecules that may include one or a combination of 4-, 5-, 6- and 7-membered rings in their skeletons.
- the conjunct polymers deactivate the chloroaluminate ionic liquid catalysts by weakening the acid strength of the catalyst through the formation of complexes of conjunct polymers and AlCl 3 possibly by means of electron-donor/electron-acceptor interactions.
- the conjunct polymers with their double bonds are the donors and the Lewis acid (AlCl 3 ) is the acceptor.
- the conjunct polymers coordinate to the Lewis acid (AlCl 3 ) in the ionic liquid and rendering the butylpyridinium chloroaluminate catalyst less active.
- the acidity of the catalyst becomes weaker and the overall catalytic activity becomes compromised and no longer effective for the intended purpose.
- the catalyst performance will become a function of the concentration of conjunct polymers in the ionic liquid phase. As more conjunct polymers accumulate in the ionic liquid phase the catalyst becomes less active. So, removal of all or a suitable portion of the conjunct polymers from the ionic liquid phase is a significant aspect of the present process for ionic liquids catalyst regeneration.
- connection polymer as used herein also includes any other species which might complex to AlCl 3 by pi bonding or sigma bonding or other means, which results in those species binding to the ionic liquid, so they are not removable by simple hydrocarbon extraction.
- Conjunct polymers isolated from the catalyst phase by means of hydrolysis are highly soluble in hydrocarbons. However, attempts to remove them from the catalyst phase prior to hydrolysis by simple extraction methods with hydrocarbon solvents such as hexane, decane and toluene were unsuccessful. Other more polar solvents such as CH 2 Cl 2 may dissolve a chloroaluminate ionic liquid and therefore are not selective solvents for dissolving and removing conjunct polymers. Conjunct polymers may be isolated by hydrolysis. However, these methods of isolating the conjunct polymers are destructive, and result in an actual loss of a catalytic component (AlCl 3 ).
- the hydrolysis methods hydrolyze the catalytic component (AlCl 3 ) and transform it into inactive aluminum hydroxide and aluminum oxide. This indicates that the conjunct polymers are tightly held in the ionic liquid phase by fairly strong type of bonding system. Therefore, any successful attempt to reactivate and regenerate the catalyst must involve the removal of conjunct polymers to release aluminum trichloride from the AlCl 3 ⁇ conjunct polymer complexes without destroying, consuming, or irreversibly tying up the AlCl 3 .
- one objective is to free the catalyst by replacing the conjunct polymers with other basic species that simply displace the polymer without destroying the catalyst or by suppressing the ability of conjunct polymers to form complexes with Lewis acids (aluminum chloride).
- the deactivated catalyst can be revived in a nondestructive manner by freeing up the AlCl 3 from conjunct polymer- AlCl 3 complex. AlCl 3 no longer bound by conjunct polymers is then released to take part in catalytic reactions.
- the present invention provides a process for the regeneration of used acidic ionic liquid catalysts in a nondestructive manner by contacting a used ionic liquid catalyst with at least one metal catalyst under regeneration conditions in the presence of added hydrogen so as to increase the activity of the used ionic liquid catalyst.
- the used ionic liquid contacts the regeneration metal in the presence of added hydrogen.
- Hydrogen pressures used may vary from quite low to very high values, typically from about 100 to 2,500 psig.
- the metal used for regeneration in this invention is preferably selected from Group III-A and II-B.
- Specific examples of the metal catalysts are B, Al, Ga, In, TI, Zn, Cd, Cu, Ag and Au. These metals may be used in any form, alone, in combination or as alloys.
- the regeneration metal may be used with other substances such as an inorganic oxide catalyst supports.
- the metals may be in the form of fine particles, granules, sponges, gauzes, etc.
- Each metal may be used in any number of forms: (1) macroscopic, which includes wires, foils, fine particles, sponges, gauzes, granules, etc.; and (2) microscopic, which includes powders, smokes, colloidal suspensions, and condensed metal films.
- the amount of metal, say aluminum, added in the regeneration scheme is determined by the amount (concentration) of the conjunct polymers in the spent ionic liquid catalyst.
- the amount of metal used for the regeneration of a given spent catalyst is usually added in excess to the concentration of conjunct polymers present in the spent catalyst.
- the metal selection for the regeneration is based on the composition of the ionic liquid catalyst.
- the metal should be selected carefully to prevent the contamination of the catalyst with unwanted metal complexes or intermediates that may form and remain in the ionic liquid catalyst phase.
- aluminum metal will be the metal of choice for the regeneration when the catalyst system is chloroaluminate ionic liquid-based catalyst.
- the use of any other metal may change the overall composition of the catalyst.
- ionic liquid catalysts may become deactivated during use.
- light (C 2 -C 5 ) olefins and isoparaffin feeds are contacted in the presence of a catalyst that promotes the alkylation reaction.
- this catalyst is a chloroaluminate ionic liquid.
- the reactor which may be a stirred tank or other type of contactor (e.g., riser reactor), produces a biphasic mixture of alkylate hydrocarbons, unreacted isoparaffins, and ionic liquid catalyst containing some conjunct polymers.
- the dense catalyst/conjunct polymer phase may be separated from the hydrocarbons by gravity settling in a decanter.
- This catalyst will be partially deactivated by the conjunct polymers binding to AlCl 3 .
- the recovered catalyst can be reactivated in a regeneration scheme in the presence of added hydrogen and a metal catalyst.
- the products of this step will be reactivated catalyst and removable conjunct polymers among others as described herein.
- the reactivated catalyst and the conjunct polymers can be separated now, for example, by solvent extraction, decantation, and filtration.
- a used ionic liquid catalyst/conjunct polymer mixture is introduced continuously into a regeneration reactor, which contains a regeneration metal.
- Hydrogen gas and inert hydrocarbons in which conjunct polymers are soluble are fed into the reactor at the desired rate.
- the inert hydrocarbons may be a normal hydrocarbons ranging from C 5 -C 15 and their mixtures, preferably C 5 -C 8 although other hydrocarbons may be employed.
- the residence time, temperature and pressure of the reactor will be selected to allow the desired reactivation of the ionic liquid catalyst.
- the reaction product is withdrawn and sent to a separator.
- This mixture is then separated into three streams, one comprising hydrogen and light hydrocarbons, a second comprising inert hydrocarbons and removable conjunct polymers and a third comprising regenerated ionic liquid catalyst.
- a gravity decanter is used to separate the mixture, from which the ionic liquid phase, which is denser than other components, is withdrawn.
- the reactivated ionic liquid catalyst is returned to the alkylation reactor.
- the solvent/conjunct polymer mix is separated by distillation to recover the solvent.
- Regeneration conditions will generally include temperatures of ⁇ 20° C.-200° C., preferably 50°-100° C. pressures of atmospheric-5000 psig, preferably 50-500 psig, and a contact time of 0.1 minute-24 hours, and preferably from 1 ⁇ 2-2 hours in a normal hydrocarbon as a solvent. Hydrogen pressures used may vary from quite low to very high values, typically from about 100 to 2,500 psig.
- 1-butyl-pyridinium chloroaluminate is a room temperature ionic liquid prepared by mixing neat 1-butyl-pyridinium chloride (a solid) with neat solid aluminum trichloride in an inert atmosphere. The syntheses of butylpyridinium chloride and the corresponding 1-butyl-pyridinium chloroaluminate are described below.
- 400 gm (5.05 mol.) anhydrous pyridine (99.9% pure purchased from Aldrich) were mixed with 650 gm (7 mol.) 1-chlorobutane (99.5% pure purchased from Aldrich). The neat mixture was sealed and let to stir at 125° C.
- 1-butylpyridinium chloroaluminate was prepared by slowly mixing dried 1-butylpyridinium chloride and anhydrous aluminum chloride (AlCl 3 ) according to the following procedure.
- the 1-butylpyridinium chloride (prepared as described above) was dried under vacuum at 80° C. for 48 hours to get rid of residual water (1-butylpyridinium chloride is hydroscopic and readily absorbs water from exposure to air).
- Five hundred grams (2.91 mol.) of the dried 1-butylpyridinium chloride were transferred to a 2-Liter beaker in a nitrogen atmosphere in a glove box.
- 1-butylpyridinium chloroaluminate ionic liquid catalyst was prepared from “fresh” 1-butylpyridinium chloroaluminate ionic liquid catalyst by carrying out the isobutane alkylation reaction in a continuous flow microunit under catalyst recycle with accelerated fouling conditions.
- the microunit consists of feed pumps for isobutane and butenes, a stirred autoclave reactor, a back pressure regulator, a three phase separator, and a third pump to recycle the separated ionic liquid catalyst back to the reactor.
- the reactor was operated at 80 to 100 psig pressure and with cooling to maintain a reaction temperature of ⁇ 10° C.
- isobutane, butenes, and HCl were pumped into the autoclave at the desired molar ratio (isobutane/butenes>1.0), through the back pressure regulator, and into the three phase separator.
- the wt % of conjunct polymers in the spent (deactivated) ionic liquid was determined by hydrolysis of known weights of the spent catalyst.
- the example below is a typical procedure for measuring conjunct polymers in a given spent catalyst.
- 15 gm of a spent ionic liquid catalyst in a flask were rinsed first with 30-50 ml of anhydrous hexane to remove (from the spent catalyst) any residual hydrocarbon or olefinic oligomers.
- the hexane rinse was concentrated under reduced pressure to give only 0.02 gm of yellow oil (0.13%).
- the recovered conjunct polymers according to the procedure described in Example 3 were characterized by elemental analysis and by infrared, NMR, GC-Mass and UV and spectroscopy methods.
- the recovered conjunct polymers have hydrogen/carbon ratio of 1.76 and chlorine content of 0.8%.
- 1 H-NMR and 13 C-NMR showed the presence of olefinic protons and olefinic carbons.
- Infra Red indicated the presence of olefinic regions and the presence of cyclic systems and substituted double bonds.
- GCMS showed the conjunct polymers to have molecular weights ranging from 150-mid 600 s.
- the recovered conjunct polymers have boiling ranges of 350-1100° F. as indicated by high boiling simulated distillation analysis.
- UV spectroscopy showed a UV ⁇ max at 250 nm pointing highly conjugated double bonds systems.
- a 300 cc autoclave was charged with 51 gm of used (deactivated) butylpyridinium chloroaluminate ionic liquid containing 12.4 wt % (6.32 gm) conjunct polymers, 65 ml hexane, and 8 gm aluminum powder.
- the autoclave was pressurized to 500 psi of hydrogen gas and heated to 100° C. while stirring with an overhead stirrer at ⁇ 1200 rpm. The pressure was kept at around 550 psi by continuously re-introducing hydrogen gas.
- the reaction was allowed to run for 1.5 hrs at the conditions stated above.
- the reaction was cooled down, and the reaction mixture was separated in the glove box where the organic layer was removed by decantation.
- the ionic liquid-aluminum residue was rinsed with 2 ⁇ 50 ml anhydrous hexane.
- the hexane layers were all combined and dried over MgSO 4 . Filtration and concentration of the dried hexane rinses gave 6.3 gm 99.7% of the expected conjunct polymers as pale yellow oils.
- the ionic liquid catalyst was separated from aluminum by filtration. Hydrolysis of 10 gm portion of the filtered ionic liquid catalyst followed by extraction with hexane showed no presence of conjunct polymers in the treated spent ionic liquid. The reaction described above was repeated once more on the same spent catalyst and led to the removal of >98% of the conjunct polymers.
- a 300 cc autoclave was charged with 51 gm of deactivated butylpyridinium chloroaluminate ionic liquid containing 12.4 wt % (6.32 gm) conjunct polymers, 60 ml hexane, 4 gm of aluminum metal and 4 gm of nickel metal powders.
- the autoclave was pressurized to 500 psi of hydrogen gas and heated to 100° C. while stirring with an overhead stirrer at >1200 rpm.
- the pressure of the reaction rose gradually to 660 psi as the reaction was heating up to 100° C. and remained there the remainder of the reaction.
- the reaction ran for 1.5 hrs at the conditions stated above.
- the autoclave was then cooled down, and the reaction mixture was separated in the glove box where the organic layer was removed by decantation.
- the ionic liquid-aluminum residue was rinsed with 2 ⁇ 50 ml anhydrous hexane.
- the hexane layers were all combined and dried over MgSO 4 . Filtration and concentration of the dried hexane rinses gave 6.15 gm (98%) of the expected hydrogenated conjunct polymers as pale yellow oils.
- the ionic liquid catalyst was separated from aluminum by filtration. Hydrolysis of 10 gm portion of the filtered ionic liquid catalyst followed by extraction with hexane showed no presence of conjunct polymers in the treated spent ionic liquid.
- Example 5 was repeated but using boron in place of aluminum to remove conjunct polymers from 50.2 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 15.3% conjunct polymers.
- the use of boron resulted in the removal of only 9% of the conjunct polymers present in the used catalyst based on the recovered polymers from the organic layer. Hydrolysis of the residual ionic liquid catalyst indicated that >89% of the conjunct polymers remained in the treated catalyst.
- Example 5 The procedure described in Example 5 was repeated but using gallium metal in place of aluminum to remove the conjunct polymers from 50.2 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 15.3% conjunct polymers.
- the reaction resulted in the removal of 52% of the conjunct polymers based on the recovered oils in the organic phase.
- Hydrolysis of the residual ionic liquid catalyst indicated that 35% of the conjunct polymers remained in the treated catalyst.
- the remaining ⁇ 13% polymers were perhaps lost during concentration of the organic solvent (hexane) as light hydrocarbons due to decomposition and fragmentation of the conjunct polymers.
- Example 5 The procedure described in Example 5 was repeated but using indium metal in place of aluminum to remove the conjunct polymers from 51 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 24.4% conjunct polymers. The reaction resulted in total removal of ⁇ 88% of the conjunct polymers based on the recovery of heavy oils in the organic phase. Hydrolysis of the residual ionic liquid catalyst indicated that 10% of the conjunct polymers remained in the treated catalyst.
- Example 5 The procedure described in Example 5 was repeated but using zinc metal powder in place of aluminum powder to remove the conjunct polymers from 50 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 24.4% conjunct polymers. The reaction resulted in the removal of ⁇ 73% of the conjunct polymers based on the recovered oils in the organic phase. Hydrolysis of the residual ionic liquid catalyst indicated that ⁇ 27% of the conjunct polymers remained in the treated catalyst.
- Example 5 The procedure described in Example 5 was repeated but using copper metal in place of aluminum to remove the conjunct polymers from 50.5 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 15.3% conjunct polymers.
- the reaction resulted in the removal of 8% of the conjunct polymers based on the recovery of heavy oils in the organic phase.
- Hydrolysis of the residual ionic liquid catalyst indicated that 82% of the conjunct polymers remained in the treated catalyst.
- the remaining 10% of the conjunct polymers were perhaps lost during concentration as light hydrocarbons due to decomposition and fragmentation of the conjunct polymers.
- Example 5 was repeated but using iron powder in place of aluminum powder to remove the conjunct polymers from 50.4 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 15.3% conjunct polymers.
- the use of iron resulted in the removal of 10% of the conjunct polymers present in the used catalyst.
- Hydrolysis of the residual ionic liquid catalyst indicated that 83% of the conjunct polymers remained in the treated catalyst. The remaining 7% of the conjunct polymers may have been lost during the concentration under vacuum as light product resulting from degradation and structural changes of conjunct polymers.
- Example 5 The procedure described in Example 5 was repeated but using titanium metal in place of aluminum to remove conjunct polymers from 51 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 15.3% conjunct polymers. The reaction resulted in the removal of 5.5% of the conjunct polymers based on the recovery of heavy oils in the organic phase. Hydrolysis of the residual ionic liquid catalyst indicated that 79% of the conjunct polymers remained in the treated catalyst. The remaining 15.5% of the conjunct polymers were perhaps lost as light hydrocarbons during evaporation due to decomposition and fragmentation reactions.
- Table 1 compares the results of removing conjunct polymers from the spent ionic liquid catalyst (used butylpyridinium chloroaluminate) by treatment with the different metals discussed in Examples 5-13.
- the activity of the regenerated catalyst was checked by comparing its activity with the activities of the spent and freshly-made catalysts in the alkylation of isopentane with ethylene.
- the alkylation of isopentane with ethylene was done according to the procedure describe below.
- a 300 cc autoclave is charged with 20 gm of ionic liquid catalyst, 100 gm anhydrous isopentane, 10 gm ethylene and 0.3 gm anhydrous HCl.
- the reaction was then stirred ⁇ 1200 rpm and heated to 50° C. at autogenic pressures.
- the starting pressure is usually 280-320 psi.
- the reaction is usually terminated when the pressure drops down to single digits or no further drop in the pressure is noticed.
- reaction In the case of slow going reaction, the reaction was allowed to go on for 1 hr. At the end of the reaction, the reaction is vented out and a gas sample is checked by GC for ethylene concentration. The reaction mixture is let to settle into 2 phases. The organic phase is decanted and analyzed for product distribution by GC analysis.
- Table 2 compares the activity of the regenerated ionic liquid catalyst over aluminum in a batch reaction with the activities of the freshly-made catalyst and the spent catalyst.
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Abstract
Description
- This application is a divisional of U.S. patent application Ser. No. 12/099,486, published as US20090253572A1, and herein incorporated in its entirety. U.S. patent application Ser. No. 12/099,486 is a continuation in part of co-pending U.S. Patent Publication Numbers 20070142214 and 20070142217; both filed on Dec. 20, 2005, and herein incorporated in their entireties. The assigned art unit of U.S. patent application Ser. No. 12/099,486 is 1793.
- The present invention relates to methods for the regeneration of catalysts and more specifically to the regeneration of ionic liquid catalysts.
- Ionic liquids are liquids that are composed entirely of ions. The so-called “low temperature” Ionic liquids are generally organic salts with melting points under 100 degrees C., often even lower than room temperature. Ionic liquids may be suitable for example for use as a catalyst and as a solvent in alkylation and polymerization reactions as well as in dimerization, oligomerization acetylation, metatheses, and copolymerization reactions.
- One class of ionic liquids is fused salt compositions, which are molten at low temperature and are useful as catalysts, solvents and electrolytes. Such compositions are mixtures of components which are liquid at temperatures below the individual melting points of the components.
- Ionic liquids can be defined as liquids whose make-up is entirely comprised of ions as a combination of cations and anions. The most common ionic liquids are those prepared from organic-based cations and inorganic or organic anions. The most common organic cations are ammonium cations, but phosphonium and sulphonium cations are also frequently used. Ionic liquids of pyridinium and imidazolium are perhaps the most commonly used cations. Anions include, but not limited to, BE4 −, PF6 −, haloaluminates such as Al2Cl7 − and Al2Br7 −, [(CF3SO2)2N)]−, alkyl sulphates (RSO3 −), carboxylates (RCO2 −) and many other. The most catalytically interesting ionic liquids are those derived from ammonium halides and Lewis acids (such as AlCl3, TiCl4, SnCl4, FeCl3 . . . etc). Chloroaluminate ionic liquids are perhaps the most commonly used ionic liquid catalyst systems.
- Examples of such low temperature ionic liquids or molten fused salts are the chloroaluminate salts. Alkyl imidazolium or pyridinium salts, for example, can be mixed with aluminum trichloride (AlCl3) to form the fused chloroaluminate salts. The use of the fused salts of 1-alkylpyridinium chloride and aluminum trichloride as electrolytes is discussed in U.S. Pat. No. 4,122,245. Other patents which discuss the use of fused salts from aluminum trichloride and alkylimidazolium halides as electrolytes are U.S. Pat. Nos. 4,463,071 and 4,463,072.
- U.S. Pat. No. 5,104,840 to describes ionic liquids which comprise at least one alkylaluminum dihalide and at least one quaternary ammonium halide and/or at least one quaternary ammonium phosphonium halide and their uses as solvents in catalytic reactions.
- U.S. Pat. No. 6,096,680 describes liquid clathrate compositions useful as reusable aluminum catalysts in Friedel-Crafts reactions. In one embodiment, the liquid clathrate composition is formed from constituents comprising (i) at least one aluminum trihalide, (ii) at least one salt selected from alkali metal halide, alkaline earth metal halide, alkali metal pseudohalide, quaternary ammonium salt, quaternary phosphonium salt, or ternary sulfonium salt, or a mixture of any two or more of the foregoing, and (iii) at least one aromatic hydrocarbon compound.
- Aluminum-containing catalysts are among the most common Lewis acid catalysts employed in Friedel-Crafts reactions. Friedel-Crafts reactions are reactions which fall within the broader category of electrophylic substitution reactions including alkylations.
- Other examples of ionic liquids and their methods of preparation may also be found in U.S. Pat. Nos. 5,731,101; 6,797,853 and in U.S. Patent Application Publications 2004/0077914 and 2004/0133056.
- Hydrogenation in chloroaluminate ionic liquids in the presence of an electropositive metal and HCl was reported by K. R. Seddon et al in Chem. Commun., 1999, 1043-1044.
- As a result of use, ionic liquid catalysts become deactivated, i.e. lose activity, and may eventually need to be replaced. However, ionic liquid catalysts are expensive and replacement adds significantly to operating expenses by in some cases requiring shut down of an industrial process. One of the heretofore unsolved problems impeding the commercial use of chloroaluminate ionic liquid catalysts has been the inability to regenerate and recycle them. The present invention provides methods to regenerate acidic chloroaluminate ionic liquid catalysts overcoming this obstacle and paving the way for the practical, commercial use of these environmentally friendly catalysts.
- The present invention, among other things, provides a process for regenerating a used acidic ionic liquid catalyst comprising contacting the used ionic liquid catalyst with at least one metal in a regeneration zone in the presence of added hydrogen under regeneration conditions for a time sufficient to increase the activity of the ionic liquid catalyst. In one embodiment, regeneration is conducted in the presence of a hydrocarbon solvent.
- The present invention relates to a process for the regeneration of spent or deactivated acidic ionic liquid-based catalysts i.e. those catalysts which have lost all or some of their catalytic activity. The present process is being described and exemplified with reference certain specific ionic liquid catalysts and processes catalyzed thereby, but such description is not intended to limit the scope of the invention. The methods described may be applied to other catalysts and processes by those persons having ordinary skill based on the teachings, descriptions and examples included herein.
- The specific examples used herein refer to alkylation processes using ionic liquid systems, which are amine-based cationic species mixed with aluminum chloride. In such systems, to obtain the appropriate acidity suitable for the alkylation chemistry, the ionic liquid catalyst is generally prepared to full acidity strength by mixing one molar part of the appropriate ammonium chloride with two molar parts of aluminum chloride. The catalyst exemplified for the alkylation process is a1-alkyl-pyridinium chloroaluminate, such as 1-butyl-pyridinium heptachloroaluminate.
- In general, a strongly acidic ionic liquid is necessary for isoparaffin alkylation, e.g. isoparaffin alkylation. In that case, aluminum chloride, which is a strong Lewis acid in a combination with a small concentration of a Broensted acid, is a preferred catalyst component in the ionic liquid catalyst scheme.
- While not being bound to this or any other theory of operation, the present invention is based in part on our discovery that one of the major catalyst deactivation mechanisms is the formation of by-products known as conjunct polymers. The term conjunct polymer was first used by Pines and Ipatieff to distinguish these polymeric molecules from the usual polymers. Unlike typical polymers, conjunct polymers are polyunsaturated cyclic, polycyclic and acyclic molecules formed by concurrent acid-catalyzed reactions including, among others, polymerization, alkylation, cyclization, and hydride transfer reactions. Conjunct polymers consist of unsaturated intricate network of molecules that may include one or a combination of 4-, 5-, 6- and 7-membered rings in their skeletons. Some examples of the likely polymeric species were reported by Miron et al. (Journal of chemical and Engineering Data, 1963) and Pines (Chem. Tech, 1982). These molecules contain double and conjugated double bonds in intricate structures containing a combination of cyclic and acyclic skeletons.
- The conjunct polymers deactivate the chloroaluminate ionic liquid catalysts by weakening the acid strength of the catalyst through the formation of complexes of conjunct polymers and AlCl3 possibly by means of electron-donor/electron-acceptor interactions. The conjunct polymers with their double bonds are the donors and the Lewis acid (AlCl3) is the acceptor. Using their double bonds, the conjunct polymers coordinate to the Lewis acid (AlCl3) in the ionic liquid and rendering the butylpyridinium chloroaluminate catalyst less active. Thus, the acidity of the catalyst becomes weaker and the overall catalytic activity becomes compromised and no longer effective for the intended purpose. Thus, the catalyst performance will become a function of the concentration of conjunct polymers in the ionic liquid phase. As more conjunct polymers accumulate in the ionic liquid phase the catalyst becomes less active. So, removal of all or a suitable portion of the conjunct polymers from the ionic liquid phase is a significant aspect of the present process for ionic liquids catalyst regeneration.
- The term “conjunct polymer” as used herein also includes any other species which might complex to AlCl3 by pi bonding or sigma bonding or other means, which results in those species binding to the ionic liquid, so they are not removable by simple hydrocarbon extraction.
- It is believed that deactivation of the catalyst by the presence of conjunct polymers is, in part at least, caused by coordination and complex formation between the Lewis acid AlCl3 (electron pair acceptor) and the conjunct polymers (electron donors). In such complexes, the AlCl3 is no longer available for catalysis since it is tied-up in the AlCl3-conjunct polymers complexes. AlCl3-conjunct polymers complexation may not be limited to the donor-acceptor (base-acid) mechanisms. HCl-promoted chloroaluminate ionic liquid-catalyzed alkylations lead very often to the formation of chlorinated conjunct polymers. Consequently, some of the aluminum trichloride-conjunct polymers complexes will be the result of interaction between AlCl3 and the chlorinated polymers to form R+AlCl4 − type intermediates. It also appears that the presence (or accumulation) of conjunct polymer molecules in the catalyst phase is not by virtue of being miscible in the ionic liquid phase. While conjunct polymers may be somewhat miscible in the ionic liquids, their accumulation in the catalyst phase is more likely to being bound by strong acid-base interactions or other forms of complexation rather than being soluble in the ionic liquid phase.
- Conjunct polymers isolated from the catalyst phase by means of hydrolysis are highly soluble in hydrocarbons. However, attempts to remove them from the catalyst phase prior to hydrolysis by simple extraction methods with hydrocarbon solvents such as hexane, decane and toluene were unsuccessful. Other more polar solvents such as CH2Cl2 may dissolve a chloroaluminate ionic liquid and therefore are not selective solvents for dissolving and removing conjunct polymers. Conjunct polymers may be isolated by hydrolysis. However, these methods of isolating the conjunct polymers are destructive, and result in an actual loss of a catalytic component (AlCl3). The hydrolysis methods hydrolyze the catalytic component (AlCl3) and transform it into inactive aluminum hydroxide and aluminum oxide. This indicates that the conjunct polymers are tightly held in the ionic liquid phase by fairly strong type of bonding system. Therefore, any successful attempt to reactivate and regenerate the catalyst must involve the removal of conjunct polymers to release aluminum trichloride from the AlCl3− conjunct polymer complexes without destroying, consuming, or irreversibly tying up the AlCl3. In other words, one objective is to free the catalyst by replacing the conjunct polymers with other basic species that simply displace the polymer without destroying the catalyst or by suppressing the ability of conjunct polymers to form complexes with Lewis acids (aluminum chloride).
- The deactivated catalyst can be revived in a nondestructive manner by freeing up the AlCl3 from conjunct polymer- AlCl3 complex. AlCl3 no longer bound by conjunct polymers is then released to take part in catalytic reactions.
- Among other things, the present invention provides a process for the regeneration of used acidic ionic liquid catalysts in a nondestructive manner by contacting a used ionic liquid catalyst with at least one metal catalyst under regeneration conditions in the presence of added hydrogen so as to increase the activity of the used ionic liquid catalyst.
- In accordance with the present invention, the used ionic liquid contacts the regeneration metal in the presence of added hydrogen. Hydrogen pressures used may vary from quite low to very high values, typically from about 100 to 2,500 psig.
- The metal used for regeneration in this invention is preferably selected from Group III-A and II-B. Specific examples of the metal catalysts are B, Al, Ga, In, TI, Zn, Cd, Cu, Ag and Au. These metals may be used in any form, alone, in combination or as alloys. For example, the regeneration metal may be used with other substances such as an inorganic oxide catalyst supports.
- The metals may be in the form of fine particles, granules, sponges, gauzes, etc. Each metal may be used in any number of forms: (1) macroscopic, which includes wires, foils, fine particles, sponges, gauzes, granules, etc.; and (2) microscopic, which includes powders, smokes, colloidal suspensions, and condensed metal films.
- An appropriately effective amount of metal is employed in the practice of the present invention. The amount of metal, say aluminum, added in the regeneration scheme is determined by the amount (concentration) of the conjunct polymers in the spent ionic liquid catalyst. For example, the amount of metal used for the regeneration of a given spent catalyst is usually added in excess to the concentration of conjunct polymers present in the spent catalyst.
- The metal selection for the regeneration is based on the composition of the ionic liquid catalyst. The metal should be selected carefully to prevent the contamination of the catalyst with unwanted metal complexes or intermediates that may form and remain in the ionic liquid catalyst phase. For example, aluminum metal will be the metal of choice for the regeneration when the catalyst system is chloroaluminate ionic liquid-based catalyst. The use of any other metal may change the overall composition of the catalyst.
- As noted previously, ionic liquid catalysts may become deactivated during use. For example, in an alkylate production unit, light (C2-C5) olefins and isoparaffin feeds are contacted in the presence of a catalyst that promotes the alkylation reaction. In one embodiment of a process in accordance with the present invention, this catalyst is a chloroaluminate ionic liquid. The reactor, which may be a stirred tank or other type of contactor (e.g., riser reactor), produces a biphasic mixture of alkylate hydrocarbons, unreacted isoparaffins, and ionic liquid catalyst containing some conjunct polymers. The dense catalyst/conjunct polymer phase may be separated from the hydrocarbons by gravity settling in a decanter. This catalyst will be partially deactivated by the conjunct polymers binding to AlCl3. The recovered catalyst can be reactivated in a regeneration scheme in the presence of added hydrogen and a metal catalyst. The products of this step will be reactivated catalyst and removable conjunct polymers among others as described herein. The reactivated catalyst and the conjunct polymers can be separated now, for example, by solvent extraction, decantation, and filtration.
- In one embodiment of the present invention, a used ionic liquid catalyst/conjunct polymer mixture is introduced continuously into a regeneration reactor, which contains a regeneration metal. Hydrogen gas and inert hydrocarbons in which conjunct polymers are soluble are fed into the reactor at the desired rate. The inert hydrocarbons may be a normal hydrocarbons ranging from C5-C15 and their mixtures, preferably C5-C8 although other hydrocarbons may be employed. The residence time, temperature and pressure of the reactor will be selected to allow the desired reactivation of the ionic liquid catalyst. The reaction product is withdrawn and sent to a separator. This mixture is then separated into three streams, one comprising hydrogen and light hydrocarbons, a second comprising inert hydrocarbons and removable conjunct polymers and a third comprising regenerated ionic liquid catalyst. A gravity decanter is used to separate the mixture, from which the ionic liquid phase, which is denser than other components, is withdrawn. The reactivated ionic liquid catalyst is returned to the alkylation reactor. The solvent/conjunct polymer mix is separated by distillation to recover the solvent.
- It is not necessary to regenerate the entire charge of catalyst. In some instances only a portion or slipstream of the catalyst charge is regenerated. In those instances only as much ionic liquid catalyst is regenerated as is necessary to maintain a desired level of catalyst activity in the process in which the ionic liquid is used as the catalyst.
- Regeneration conditions will generally include temperatures of −20° C.-200° C., preferably 50°-100° C. pressures of atmospheric-5000 psig, preferably 50-500 psig, and a contact time of 0.1 minute-24 hours, and preferably from ½-2 hours in a normal hydrocarbon as a solvent. Hydrogen pressures used may vary from quite low to very high values, typically from about 100 to 2,500 psig.
- The following Examples are illustrative of the present invention, but are not intended to limit the invention in any way beyond what is contained in the claims which follow.
- 1-butyl-pyridinium chloroaluminate is a room temperature ionic liquid prepared by mixing neat 1-butyl-pyridinium chloride (a solid) with neat solid aluminum trichloride in an inert atmosphere. The syntheses of butylpyridinium chloride and the corresponding 1-butyl-pyridinium chloroaluminate are described below. In a 2-L Teflon-lined autoclave, 400 gm (5.05 mol.) anhydrous pyridine (99.9% pure purchased from Aldrich) were mixed with 650 gm (7 mol.) 1-chlorobutane (99.5% pure purchased from Aldrich). The neat mixture was sealed and let to stir at 125° C. under autogenic pressure over night. After cooling off the autoclave and venting it, the reaction mix was diluted and dissolved in chloroform and transferred to a three liter round bottom flask. Concentration of the reaction mixture at reduced pressure on a rotary evaporator (in a hot water bath) to remove excess chloride, un-reacted pyridine and the chloroform solvent gave a tan solid product. Purification of the product was done by dissolving the obtained solids in hot acetone and precipitating the pure product through cooling and addition of diethyl ether. Filtering and drying under vacuum and heat on a rotary evaporator gave 750 gm (88% yields) of the desired product as an off-white shiny solid. 1H-NMR and 13C-NMR were consistent with the desired 1-butyl-pyridinium chloride and no impurities were observed.
- 1-butylpyridinium chloroaluminate was prepared by slowly mixing dried 1-butylpyridinium chloride and anhydrous aluminum chloride (AlCl3) according to the following procedure. The 1-butylpyridinium chloride (prepared as described above) was dried under vacuum at 80° C. for 48 hours to get rid of residual water (1-butylpyridinium chloride is hydroscopic and readily absorbs water from exposure to air). Five hundred grams (2.91 mol.) of the dried 1-butylpyridinium chloride were transferred to a 2-Liter beaker in a nitrogen atmosphere in a glove box. Then, 777.4 gm (5.83 mol.) of anhydrous powdered AlCl3 (99.99% from Aldrich) were added in small portions (while stirring) to control the temperature of the highly exothermic reaction. Once all the AlCl3 was added, the resulting amber-looking liquid was left to gently stir overnight in the glove box. The liquid was then filtered to remove any un-dissolved AlCl3. The resulting acidic 1-butyl-pyridinium chloroaluminate was used as the catalyst for the alkylation of isoparaffins with light olefins.
- “Deactivated” or “used” 1-butylpyridinium chloroaluminate ionic liquid catalyst was prepared from “fresh” 1-butylpyridinium chloroaluminate ionic liquid catalyst by carrying out the isobutane alkylation reaction in a continuous flow microunit under catalyst recycle with accelerated fouling conditions.
- The microunit consists of feed pumps for isobutane and butenes, a stirred autoclave reactor, a back pressure regulator, a three phase separator, and a third pump to recycle the separated ionic liquid catalyst back to the reactor. The reactor was operated at 80 to 100 psig pressure and with cooling to maintain a reaction temperature of ˜10° C. To start the reaction, isobutane, butenes, and HCl were pumped into the autoclave at the desired molar ratio (isobutane/butenes>1.0), through the back pressure regulator, and into the three phase separator. At the same time, fresh chloroaluminate ionic liquid catalyst was pumped into the reactor at a rate pre-calculated to give the desired catalyst/feed ratio on a volumetric basis. As the reaction proceeded, ionic liquid separated from the reactor effluent and collected in the bottom of the three phase separator. When a sufficient level of catalyst built up in the bottom of the separator, the flow of fresh ionic liquid was stopped and catalyst recycle from the bottom of the separator was started. In this way, the initial catalyst charge was continually used and recycled in the process.
- The following process conditions were used to generate Deactivated Catalyst A (1-butylpyridinium chloroaluminate ionic liquid catalyst) from Fresh Catalyst A:
-
Process Variable Isobutane pump rate 4.6 g/min Butene pump rate 2.2 g/min IL Catalyst pump rate 1.6 g/min HCl flow rate 3.0 SCCM pressure 100 psig temperature 10° C. - The reaction was continued for 72 hours when it was judged that the catalyst had become sufficiently deactivated.
- The wt % of conjunct polymers in the spent (deactivated) ionic liquid was determined by hydrolysis of known weights of the spent catalyst. The example below is a typical procedure for measuring conjunct polymers in a given spent catalyst. In a glove box, 15 gm of a spent ionic liquid catalyst in a flask were rinsed first with 30-50 ml of anhydrous hexane to remove (from the spent catalyst) any residual hydrocarbon or olefinic oligomers. The hexane rinse was concentrated under reduced pressure to give only 0.02 gm of yellow oil (0.13%). Then, 50 ml of anhydrous hexane was added to the rinsed catalyst followed by slow addition of 15 ml of water, and the mixture was stirred at 0° C. for 15-20 minutes. The resulting mixture was diluted with additional 30 ml hexanes and stirred well for additional 5-10 minutes. The mixture was allowed to settle down to two layers solution and some solid residue. The organic layer was recovered by decanting. The aqueous layer was further washed with additional 50 ml hexanes. The hexanes layers were combined and dried over anhydrous MgSO4, filtered and concentrated to give 2.5 gm (16.7 wt % of the spent catalyst) of viscous dark orange-reddish oil. It was determined therefore that this particular spent catalyst contains 0.13% oligomers and 16.7% conjunct polymers. The hydrolysis can also be accomplished using acidic (aqueous HCl) or basic (aqueous NaOH) solutions.
- The recovered conjunct polymers according to the procedure described in Example 3 were characterized by elemental analysis and by infrared, NMR, GC-Mass and UV and spectroscopy methods. The recovered conjunct polymers have hydrogen/carbon ratio of 1.76 and chlorine content of 0.8%. 1H-NMR and 13C-NMR showed the presence of olefinic protons and olefinic carbons. Infra Red indicated the presence of olefinic regions and the presence of cyclic systems and substituted double bonds. GCMS showed the conjunct polymers to have molecular weights ranging from 150-mid 600 s. The recovered conjunct polymers have boiling ranges of 350-1100° F. as indicated by high boiling simulated distillation analysis. UV spectroscopy showed a UV λmax at 250 nm pointing highly conjugated double bonds systems.
- A 300 cc autoclave was charged with 51 gm of used (deactivated) butylpyridinium chloroaluminate ionic liquid containing 12.4 wt % (6.32 gm) conjunct polymers, 65 ml hexane, and 8 gm aluminum powder. The autoclave was pressurized to 500 psi of hydrogen gas and heated to 100° C. while stirring with an overhead stirrer at ˜1200 rpm. The pressure was kept at around 550 psi by continuously re-introducing hydrogen gas. The reaction was allowed to run for 1.5 hrs at the conditions stated above. The reaction was cooled down, and the reaction mixture was separated in the glove box where the organic layer was removed by decantation. The ionic liquid-aluminum residue was rinsed with 2×50 ml anhydrous hexane. The hexane layers were all combined and dried over MgSO4. Filtration and concentration of the dried hexane rinses gave 6.3 gm 99.7% of the expected conjunct polymers as pale yellow oils. The ionic liquid catalyst was separated from aluminum by filtration. Hydrolysis of 10 gm portion of the filtered ionic liquid catalyst followed by extraction with hexane showed no presence of conjunct polymers in the treated spent ionic liquid. The reaction described above was repeated once more on the same spent catalyst and led to the removal of >98% of the conjunct polymers. The reaction was repeated on 52 gm of spent butyl-pyridinium chloroaluminate catalysts containing 15.5 wt % (7.9 gm CPs) and led to removing 7.8 gm of the polymers (98.7%) from the spent catalyst. There were no conjunct polymers obtained from the hydrolysis of the treated (regenerated) ionic liquid catalysts indicating the removal of all CPs from the spent catalyst. This procedure is, by far, the most successful method for removing conjunct polymers from the spent chloroaluminate ionic liquid catalysts.
- A 300 cc autoclave was charged with 51 gm of deactivated butylpyridinium chloroaluminate ionic liquid containing 12.4 wt % (6.32 gm) conjunct polymers, 60 ml hexane, 4 gm of aluminum metal and 4 gm of nickel metal powders. The autoclave was pressurized to 500 psi of hydrogen gas and heated to 100° C. while stirring with an overhead stirrer at >1200 rpm. The pressure of the reaction rose gradually to 660 psi as the reaction was heating up to 100° C. and remained there the remainder of the reaction. The reaction ran for 1.5 hrs at the conditions stated above. The autoclave was then cooled down, and the reaction mixture was separated in the glove box where the organic layer was removed by decantation. The ionic liquid-aluminum residue was rinsed with 2×50 ml anhydrous hexane. The hexane layers were all combined and dried over MgSO4. Filtration and concentration of the dried hexane rinses gave 6.15 gm (98%) of the expected hydrogenated conjunct polymers as pale yellow oils. The ionic liquid catalyst was separated from aluminum by filtration. Hydrolysis of 10 gm portion of the filtered ionic liquid catalyst followed by extraction with hexane showed no presence of conjunct polymers in the treated spent ionic liquid.
- Example 5 was repeated but using boron in place of aluminum to remove conjunct polymers from 50.2 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 15.3% conjunct polymers. The use of boron resulted in the removal of only 9% of the conjunct polymers present in the used catalyst based on the recovered polymers from the organic layer. Hydrolysis of the residual ionic liquid catalyst indicated that >89% of the conjunct polymers remained in the treated catalyst.
- The procedure described in Example 5 was repeated but using gallium metal in place of aluminum to remove the conjunct polymers from 50.2 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 15.3% conjunct polymers. The reaction resulted in the removal of 52% of the conjunct polymers based on the recovered oils in the organic phase. Hydrolysis of the residual ionic liquid catalyst indicated that 35% of the conjunct polymers remained in the treated catalyst. The remaining ˜13% polymers were perhaps lost during concentration of the organic solvent (hexane) as light hydrocarbons due to decomposition and fragmentation of the conjunct polymers.
- The procedure described in Example 5 was repeated but using indium metal in place of aluminum to remove the conjunct polymers from 51 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 24.4% conjunct polymers. The reaction resulted in total removal of ˜88% of the conjunct polymers based on the recovery of heavy oils in the organic phase. Hydrolysis of the residual ionic liquid catalyst indicated that 10% of the conjunct polymers remained in the treated catalyst.
- The procedure described in Example 5 was repeated but using zinc metal powder in place of aluminum powder to remove the conjunct polymers from 50 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 24.4% conjunct polymers. The reaction resulted in the removal of ˜73% of the conjunct polymers based on the recovered oils in the organic phase. Hydrolysis of the residual ionic liquid catalyst indicated that ˜27% of the conjunct polymers remained in the treated catalyst.
- The procedure described in Example 5 was repeated but using copper metal in place of aluminum to remove the conjunct polymers from 50.5 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 15.3% conjunct polymers. The reaction resulted in the removal of 8% of the conjunct polymers based on the recovery of heavy oils in the organic phase. Hydrolysis of the residual ionic liquid catalyst indicated that 82% of the conjunct polymers remained in the treated catalyst. The remaining 10% of the conjunct polymers were perhaps lost during concentration as light hydrocarbons due to decomposition and fragmentation of the conjunct polymers.
- Example 5 was repeated but using iron powder in place of aluminum powder to remove the conjunct polymers from 50.4 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 15.3% conjunct polymers. The use of iron resulted in the removal of 10% of the conjunct polymers present in the used catalyst. Hydrolysis of the residual ionic liquid catalyst indicated that 83% of the conjunct polymers remained in the treated catalyst. The remaining 7% of the conjunct polymers may have been lost during the concentration under vacuum as light product resulting from degradation and structural changes of conjunct polymers.
- The procedure described in Example 5 was repeated but using titanium metal in place of aluminum to remove conjunct polymers from 51 gm of spent butylpyridinium chloroaluminate ionic liquid catalyst containing 15.3% conjunct polymers. The reaction resulted in the removal of 5.5% of the conjunct polymers based on the recovery of heavy oils in the organic phase. Hydrolysis of the residual ionic liquid catalyst indicated that 79% of the conjunct polymers remained in the treated catalyst. The remaining 15.5% of the conjunct polymers were perhaps lost as light hydrocarbons during evaporation due to decomposition and fragmentation reactions.
- Table 1 below compares the results of removing conjunct polymers from the spent ionic liquid catalyst (used butylpyridinium chloroaluminate) by treatment with the different metals discussed in Examples 5-13.
-
TABLE 1 Total Hydrogen % CPS % CPS % CPS % CPs Metal (500 psi) Removed Remained Lost Removed Aluminum Yes >99% <1 0 >99 Boron Yes 9 89 2 11 Gallium Yes 52 35 13 65 Indium Yes 88 10 2 90 Al/Ni Yes 98 0 2 100 Zinc Yes 71 27 2 73 Iron Yes 10 83 7 17 Copper Yes 8 82 10 18 Titanium Yes 5.5 79 15.5 21 - Based on the results discussed in the examples above, aluminum and other metals appear to effectively remove conjunct polymers from the spent catalyst. Without being bound to any theory, it appears that the removal mechanism is probably driven by an oxidative-reductive reaction where the metal is reducing the conjunct polymers and their chlorinated analogues.
- The activity of the regenerated catalyst was checked by comparing its activity with the activities of the spent and freshly-made catalysts in the alkylation of isopentane with ethylene. The alkylation of isopentane with ethylene was done according to the procedure describe below. A 300 cc autoclave is charged with 20 gm of ionic liquid catalyst, 100 gm anhydrous isopentane, 10 gm ethylene and 0.3 gm anhydrous HCl. The reaction was then stirred ˜1200 rpm and heated to 50° C. at autogenic pressures. The starting pressure is usually 280-320 psi. The reaction is usually terminated when the pressure drops down to single digits or no further drop in the pressure is noticed. In the case of slow going reaction, the reaction was allowed to go on for 1 hr. At the end of the reaction, the reaction is vented out and a gas sample is checked by GC for ethylene concentration. The reaction mixture is let to settle into 2 phases. The organic phase is decanted and analyzed for product distribution by GC analysis.
- Table 2 compares the activity of the regenerated ionic liquid catalyst over aluminum in a batch reaction with the activities of the freshly-made catalyst and the spent catalyst.
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TABLE 2 Al/H2 Fresh Spent Regen Catalyst Catalyst Cat. Reaction Time 6 min. 60 min. 7 min. Starting 312 psi 304 298 Pressure Ending 6 psi 309 psi 5 psi pressure iC5 wt % 66.8 97.8 68.4 C7s wt %: 22.3 1.3 21.4 2,3-DM- 8.8 1 8 Pentane 2,4-DM- 9.5 0.67 8.25 Pentane 2,3-DMP/2,4- 0.93 1.51 0.97 DMP - There are numerous variations on the present invention which are possible in light of the teachings and supporting examples described herein. It is therefore understood that within the scope of the following claims, the invention may be practiced otherwise than as specifically described or exemplified herein.
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US20090253572A1 (en) | 2009-10-08 |
US7956002B2 (en) | 2011-06-07 |
US7807597B2 (en) | 2010-10-05 |
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